Insecticide formulation



Filed Dec.

01% PYRETHRINS ADDED 400 i OPTIMUM C. C. CRAWFORD ETAL INSECTICIDE FORMULATION KILL VS. BOILING RANGE )NvsA/roRs c; c. CRAWFORD L. L. JACQUIEB BY L ATTORNEYS RANGE ALKYLATE BOILING RANGE, F

Patented Nov. 13, 1951 2,575,098 msscrrcmr; FORMULATION Chester C. Crawford and Lloyd L. Jaq'uier, Jr.,

Bartlesville, Okla. leum Company,

assignors to Phillips Petroaborporation of Delaware Application December 4, 1946, Serial No. 713,902

12 Claims. (Cl. 167-22) This invention relates to improvements in insecticidal compositions containing mixtures of toxic material such as pyrethrum extract and a perfume. DDT and rotenone have also been used extensively in solution in kerosene with or without an added perfume.

It has recently been shown that substantially pure isoparaflinic base oils of similar boiling range are excellent base oils for insecticides containing such toxic materials and have the propertiesof being non-toxic to animals and plants and of causing relatively little swelling of natural or synthetic rubbers brought in contact therewith. These isoparaflinic base oils are ordinarily prepared by the alkylation of an olefin with an isoparaflin using HF, AlCla, H2804 or other suitable catalyst, or by processes involving polymerization of olefins followed by hydrogenation according to well known methods for producing high octane motor fuels. When compounds boiling in the motor fuel range are distilled from the products of such reaction a residue of higher boiling branched chain paraflins is obtained. This residue usually contains materials boiling from about 350 F. to 600 F. with a small amount of higher boiling materials. This residue is composed essentially of branched chain paraflin hydrocarbons with only very small amounts of straight chain paraiiins and contains substantially no cycloparafiins or unsaturates. Obviously such materials may be fractionated to obtain cuts of any boiling range desired and such cuts may be further treated to remove impurities, if present.

isoparaflinic cuts have insecticidal properties approximately equivalent to those of kerosene, as is shown by the tables in columns 3 and 4 of U. S. Patent 2,405,775 issued to Bradley August 13, 1946.

It is an object of this invention to provide insecticidal compositions wherein the combination of a toxic material and a selected fraction of branched chain hydrocarbons results in a synergistic increase in insecticidal power.

Another object is to provide a branched chain paraflin solvent for insecticidal material which has optimum boiling range.

. Another object is to provide a branched chain paraflin solvent which shows substantial synergistic increase in insecticidal power when employed with-many commonly used toxic materials.

Other objects and advantages will become apparent to those skilled in the art as this-disclosure proceeds.

We have discovered that certain definite fractions of branched chain paraflin hydrocarbons, substantially free from impurities when used as solvent for common toxic materials such as pyrethrins, rotenone, 2,2-bis (parachlorophenyD- 1,1,1-trichloroethane usually known as DDT," 2,2 bis (parachlorophenyl 1,1 dichloroethane also known as "DDD, benzene hexachloride and butyl carbitol thiocyanate commercially called Lethane result in solutions having greatly increased insecticidal power, as compared to acid washed kerosene fractions or other alkylate fractions containing the same proportions of the same toxic materials. We have found the inv crease in insecticidal power to be synergistic and not additive, as the most efiective fractions of branched chain parafiins are less toxic to insects than ordinary kerosene when used without added toxic materials.

'I'he'branched chain paraffin fractions which we prefer to use are prepared from heavy alkylate or other stock consisting essentially of branched chain paraflin hydrocarbons by methods shown in the copending applications of Legatski and Crawford, Serial No. 616,930, filed September 17, 1945,

It has been believed, in the prior art, that such now Patent 2,468,986, issued May 3, 1949, and

Crawford and Morris, Serial No. 617,870, filed September 21, 1945, now Patent 2,463,601, issued March 8, 1949. Such fractions are composed almost entirely of branched chain paraffin hydrocarbons, may have any boiling range desired, and are substantially free from products of hydrocarbon oxidation. However we do not wish to limit our invention to branched chain paraffin hydrocarbons prepared by the above methods. Any method may be used which results in a fraction of branched chain paraflin hydrocarbons of desired boiling range and substantially free from other materials.

The accompanying drawing shows a smooth curve representing the relative insecticidal power of solutions containing 0.1 per cent pyrethrins in various branched chain paraffin fractions. The boiling ranges of the individual fractions compared are shown by the short horizontal lines.

The 24 hour kill of the oiliclal Feet-Grady test for evaluating fly sprays is plotted against boiling range of the solvent. An optimum boiling range for branched chain paraflln solvents is shown to be from about 360 F. to 420 F. and a second wider range from 300 F. to 420 F. would give far greater killing power than any range lying outside these limits.

We prefer to use a fraction of branched chain paraffin hydrocarbons boiling in the range from 360 F. to 410 F., as such narrow boiling range provides a very uniform evaporation rate and eliminates any residual oil fllm or stain. Typical characteristics of such solvent are:

ASTM D287-39. Refractive Index. at C Corrosion (3 hrs. at 122 F.). Doctor Test Negative ASTM 13484- Kauri Butanol Number H. A. Gardner. Dimethyl Sulfate Value, per cent 2 H. A. Gardner. Bromine Number l. 2 ASTM ES-a. Viscosity, at F. Centistokes l. 61

Com arative S t Dry Time 27 Min.

Resi ual Odor est None ASTM B26844. Odor I Neutral i H. A. Gardner, Plysicol and Chemical Examination of Paint Varnish Lacquers and olors," 6 ed., 1033.

I No naphtha or kerosene odor.

A boiling range from 360 F. to 410 F. in connection with a flash point of not less than F. is probably the most outstanding physical characteristic of our preferred solvent.

We have found that considerable variation from the above characteristics may be present and the solvent will still have marked synergistic effect with commonly used toxic materials. For instance the boiling range may be widened to 300 F. to 480 F. with corresponding changes in other characteristics while lowering the synergistic effect of the solvent to only a relatively small de- 8 6- For purposes of illustration only and not with intent to limit our invention thereto, data obtained with a solvent having the characteristics set forth above are shown in the following exples.

' 0.05% Pyrethrins:

Base on o Example I Per Cent 10 Min. 0. T. 1. Kill, 24 Knock- Differ- Hours down once Base Oil A 40 8 99.1 +2.6 39 6 99.2 +1.4 43 7 99. 1 +5. 5 Base Oil D 47 O 98.9 l.7 Our Preferred Solvent 82 5 99. 1 +33. 8

Base Oil C was selected as the best of the commercially available insecticide base oils for further comparison with our preferred solvent in the preparation of insecticides.

Example II Solutions of pyrethrins in base oil C of Example I were compared with solutions of pyrethrins in our preferred solvent having the same pyrethrin content. A modified Feet-Grady Free Flying test was used. The modification consisted of the use of a chamber about three times standard size.

In all comparative determinations 30 ml. of insecticide were sprayed into a 650 cubic foot chamber. .With the exception of the use of this large chamber, standard Poet-Grady procedure was followed. The Oflicial Test Insecticide was used. The results were:

Per Cent 10 Minute Kill. 24 Knock- Hours down 23 Preferred Solvent l1 0.1'7i3lgoret3rins: 25

Example Ill Solutions of DDT," 2,2 bis(paradichlorophenyl) -1,1,l -trichloroethane, were similarly prepared and tested. The results were: I

Solutions of commercial grade chlorinated Example V Solutions of commercial grade butyl carbitol thiocyanate were similarly prepared and tested. The results were:

Per Cent 10 Minute Kill, 24 Knockr Hours down 1.0% Butyl Carbitol Thlocyanate:

Base Oil 99 Preferred Soiven 4 91 3.5% Butyl Oarbitol Thiocyana Base Oil 0 22 100 Preferred Solvent........ 53 4 100 7.0% Butyl Carbitol Thiocyanate:

BaseOil 0 63 100 Preferred Solvent 94 100 7.20% Butyl Uarbitol Thiocyanate in Base Oil 60 Oiiicial Test Insecticide. 49' 99 0.1% solutions of pyrethrins in fractions were prepared. These were tested by Feet-Grady procedure and the following results, stated in percentage of kill in 24 hours above that shown by'the Official Test Insecticide, were obtained:

Fraction boiling from 300 F. to 360 F 30.6 Fraction boiling from 360 F. to 410 F 39.5 Fraction boilingfrom 400 F. to 480' E..." 15.6

Fractions boiling above 480 F. were found to have greatly reduced killing power.

We do not know the mechanism by which increased insecticidal power results from the use of our solvents with commonly used toxic materials in insecticides. Apparently it results from effect of the solvent. The solvents described are relatively non-toxic to human beings and do not noticeably irritate the eyes, nose or skin.

We claim:

1. An insecticide consisting essentially of a mixture of branched chain paraflinhydrocarbons having the following characteristics:

- Test Re- Properties Suns Test Method Distillation (760 mm.) ASTM D8645.

{3P F 268 72 w 313 375 7 377 384 389 E1 403 Specific Gravity, at 60/60 F... 0. 7649 ASTM D287-39. Refractive Index, at 20 0.. l. 4242 AS'IM ES-a. Flash Point (TOO), F-. 143 ASTM D56-36. Bromine Number.-. 1. 2 ASTM ES-45a. ResidualOdor Test. None ASTM D268-44. Odor 1 Neutral 1 No naphtha or kerosene odor.

and dissolved therein 0.1% to 7% by weight of an insect poison soluble in said mixture of branched chain paraflins, characterized by the property of having a higher insecticidal power than an insecticide of the same concentration of said insect poison dissolved in a kerosene.

"2. The insecticide of claim 1 in which said insect poison is 2,2-bis(parachlorophenyl) -1,1,1- trichloroethane present in an amount equal to from 0.05 to 0.2 per cent.

3. The insecticide of claim 1 in which said insect poison is pyrethrins present in an amount equal to from 0.1 to 0.2 per cent.

4. The insecticide of claim 1 in which said insect poison is butyl carbitol thiocyanate present in an amount equal to from 1 to 7 per cent.

5. An insecticide consisting essentially of a mixture of branched chain parrafiln hydrocarbons the high percentages of secondary and/or tertiary carbon atoms present in such solvents, but we do not wish to be limited to any theory of chemical or physiological action. The synergistic action containing secondary and tertiary carbon atoms and produced by synthesis from lower-boiling aliphatic hydrocarbons, and boiling in the range from 360 F. to 410 F., and dissolved therein 0.025 to 7 per cent of an insect poison soluble in said mixture of branched-chain paraflins, characterized by the property of having a higher insecticidal power than an insecticide of the same concentration of said insect poison dissolved in a kerosene.

6. An improved insecticide comprising at least 93 per cent by weight of a mixture of branched chain paraffin hydrocarbons boiling in the range from 360 F. to 410 F., said mixture having the property of increasing the insecticidal power of an insect poison dissolved therein as contrasted with the lack of such a property in a kerosene insecticide solvent; and at least 0.025 per cent by weight of at least one insect poison soluble in said mixture of branched chain paraflin hydrocarbons.

7. The insecticide of claim 6, wherein said insect poison is DDT, 2,2-bis(paradichlorophenyl)1,1,1-trichloroethane, which is present in an amount of at least 0.05 per cent by weight.

8. The insecticide of claim 6, wherein said insect poison is pyrethrin which is present in an amount of at least 0.1 per cent by weight.

9. The insecticide of claim 6, wherein said insect poison is chlorinated naphthalene.

making masking materialsunnecessary, but these may be used if desired without decreasing the 10. The insecticide of claim 6, wherein said insectpoison is butyl carbitol thiocyanate which is present in an amount of at least 3.6 per cent by weight.

11. The insecticide 01' claim 6, wherein said insect poison is rotenone.

12, An improved insecticide consisting essentiallyof a mixture of branched chain paraflin hydrocarbons boiling in the'range from 360 F. to 410 F., said mixture having the property of increasing the insecticidal power 01' an insect poison dissolved therein as contrasted with the lack of such a property in a kerosene insecticide solvent; and at least one insect poison soluble in said mixture oi branched chain paramn hydrocarbons.

CHESTER. C. CRAWFORD. LLOYD L. JACQUIER. JR.

REFERENCES CITED The following references are of record in the file of this patent: 1

UNITED STATES PATENTS Name Number Date Barber Apr. 1c, 1926 Number Number Name Date Heckert June 9, 1931 Grant Oct. 16, 1934 Donlan Oct. 25, 1937 O'Kane Aug 23, 1938 App Nov. 19, 1940 Brown June 8, 1943 Marschner Oct. 10, 1944 Frey -8ept. 11, 1945 Jones 4 Mar. 19, 1946 Boedeker et a1. Mar. 26, 1946 Bradley Aug. 13, 1946 Upham Apr. 1, 1947 Frey et ai. July 27, 1948 Beman et a1. Mar. 28, 1950 FOREIGN PATENTS I Country Date Great Britain Feb. 9, 1944 OTHER REFERENCES Roark, Chemical and Engineering News, vol. 22, N0. 17, Sept. 10, 1944, pages 1466-1468.

Heat Engineering, July 1941. p. 106. 

12. AN IMPROVED INSECTICIDE CONSISTING ESSENTIALLY OF A MIXTURE OF BRANCHED CHAIN PARAFFIN HYDROCARBONS BOILING IN THE RANGE FROM 360* F. TO 410* F., SAID MIXTURE HAVING THE PROPERTY OF INCREASING THE INSECTICIDAL POWER OF AN INSECT POISON DISSOLVED THEREIN AS CONTRASTED WITH THE LACK OF SUCH A PROPERTY IN A KEROSENE INSECTICIDE SOLVENT; AND AT LEAST ONE INSECT POISON SOLUBLE IN SAID MIXTURE OF BRANCHED CHAIN PARAFFIN HYDROCARBONS. 